Compounds and methods for controlling fungi, bacteria and insects

ABSTRACT

The present invention includes compounds of pyridinium salts and methods of their use for industrial uses. The present invention also relates to methods of controlling fungi and/or bacteria. The present invention may also be used to control insects.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.10/792,496, filed Mar. 3, 2004 now U.S. Pat. No. 7,220,761, and claimspriority to U.S. Provisional Application No. 60/480,995, filed on Jun.23, 2003, U.S. Provisional Application No. 60/524,775, filed on Nov. 25,2003, U.S. Provisional Application No. 60/525,075, filed on Nov. 25,2003, U.S. Provisional Application No. 60/524,784, filed on Nov. 25,2003, and U.S. Provisional Application No. 60/450,599, filed on Mar. 3,2003. The disclosures of each are incorporated herein by reference intheir entireties.

FIELD OF THE INVENTION

The present invention generally relates to methods of controlling fungiand/or bacteria. More specifically the present invention relates tocontrolling fungal or bacterial infestations relating to industrialuses. The present invention may also be used to control insects.

BACKGROUND OF THE INVENTION

Vast demands exist for compounds to control microorganisms in fieldsother than agriculture. These include the treatment of fabrics toprevent mildew and rot; to inhibit and kill bacterial growth; thetreatment of surfaces and substrates to obtain antiseptic conditions formedical, industrial, food processing and household purposes; thetreatment of wood for decking or building; the formulation of ink andpaints to prevent mold growth and bacterial decomposition; theprevention and treatment of human and animal diseases; and on through analmost infinite spectrum of applications touching our daily lives.

Fungi includes organisms such as slime molds, mushrooms, smuts, rusts,mildews, molds, stinkhorns, puffballs, truffles and yeasts. Fungi areclassified in their own kingdom because they absorb food in solutiondirectly through their cell walls and reproduce through spores. Moldsare a large group of fungi that are a common trigger for allergies.Molds can exist as tiny particles called “mold spores” present in indoorand outdoor air. There are more than 100,000 species in the world. Moldsmay grow anywhere they can find moisture sources. Common molds includeCladosporium, Penicillium, Aspergillus, Alternaria, Fusarium,Stachybotyrs and Mucor.

Mold has been around forever but only recently has it began to support abillion dollar industry of remediation contractors, consultants,laboratories, physicians and attorneys—as evidenced by an explosion ofmulti-million dollar lawsuits for property damage and personal injury.In Ballard v. Farmers Insurance case, a jury awarded a Texas homeowner$32.1 million, consisting of $6.2 million for remediation or replacementcost of the property damaged as well as living expenses; $12 million inpunitive damages; $5 million for emotional distress damages; and $8.9million in attorneys' fees and costs, for mold damage to the residence.Thus, there is a need to reduce mold in buildings and homes.

There is a continuing need for new antibacterial agents. Although manycompounds are known which are useful in the treatment of Gram-positiveand Gram-negative bacterial infections as well as other microbialinfections, the widespread use of such compounds continues to give riseto resistant strains of microorganisms, i.e., strains of microorganismsagainst which a particular antibiotic or group of antibiotics, andchemical compositions which was previously effective, is no longeruseful. Also, known antibiotics and chemical compositions may beeffective against only certain strains of microorganisms or have limitedactivity against either Gram-positive or Gram-negative, aerobic oranaerobic organisms.

Stilbazium iodide is a known anthelmintic which is reported to beeffective against roundworms, threadworms, and whipworms. U.S. Pat. No.3,075,975 and 3,085,935 recite methods of eradicating infestations ofparasitic nematodes inhabiting the intestinal tract.

SUMMARY OF THE PRESENT INVENTION

The present invention relates to methods and compositions comprisingstilbazium. One aspect of the present invention is a compositioncomprising formula (I)

or a solvate thereof wherein said compound is substantially in the E, Econfiguration The amino moieties may be in either the ortho, meta orpara postion. X⁻ may be an anionic salt, R₁, R₂, R₃, or R₄ areindependently selected from the group consisting of methyl, ethyl, C₁₋₁₀alkyl (linear or branched), alkenes (linear or branched), or wherein R₁and R₂ or R₃ and R₄ taken together with the nitrogen atom to which theyare attached form pyrrolidino or piperidino rings; and R₅ is selectedfrom the group consisting of methyl, ethyl, C₁₋₁₀ alkyl (linear orbranched), alkenes (linear or branched), alkynes, n-propyl, i-propyl,n-butyl, i-butyl, substituted and unsubstituted aryl moieties andsubstituted and unsubstituted benzyl moieties. The substituted andunsubstituted aryl moieties and substituted and unsubstituted benzylmoieties may include, but are not limited to lower alkyl, aryl, benzyl,acyl, amido, amino, alkoxy, carboxy, carboxy ester, alcohol, nitro,trifluoroalkoxy, trifluoroalkyl and halo. R₅ may also be anorganometallic compound such as organotin, organosilicon, ororganogermanium. Additionally, R₅ may be (CH₂)_(n)-MR₆, wherein n is anumber from 1 to 6, M is an organometallic compound such as tin,silicon, or germanium, and wherein R₆ is a selected from the groupconsisting of propyl, butyl, or any alkyl compound.

The present invention also relates to methods of controlling fungiand/or bacteria comprising administering a composition comprising any ofthe below formulas or a solvate thereof.

or a solvate thereof, wherein X⁻ is an anionic salt, wherein R₁, R₂, R₃,or R₄ are independently selected from the group consisting of methyl,ethyl, C₁₋₁₀ alkyl, linear or branched, alkenes, or wherein when R₁ andR₂ or when R₃ and R₄ are taken together with the nitrogen atom to whichthey are attached, they form pyrrolidino or piperidino rings. R₅ isselected from the group consisting of methyl, ethyl, C₁₋₁₀ alkyl, linearor branched, alkenes, alkynes, n-propyl, i-propyl, n-butyl, i-butyl,substituted and unsubstituted aryl moieties and substituted andunsubstituted benzyl moieties. R₅ may also be an organometallic compoundsuch as organotin, organosilicon, or organogermanium. Additionally, R₅may be (CH₂)_(n)-MR₆, wherein n is a number from 1 to 6, M is anorganometallic compound such as tin, silicon, or germanium, and whereinR₆ is a selected from the group consisting of propyl, butyl, or anyalkyl compound. The present compound is more commonly known asstilbazium.

The present invention also relates to methods of controlling insectscomprising administering a composition comprising any of the aboveformulas or a solvate thereof.

The present invention also relates to microcapsule compositions that arestabilized against environmental degradation.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-1G show various compounds including a methyl on a pyridine ringat the nitrogen position.

FIGS. 2A-2G depict various compounds including a trifluoroethyl attachedto the pyridine ring at the nitrogen position.

FIGS. 3A-3F illustrate compounds including an isobutyl on the pyridinering at the nitrogen position.

FIGS. 4A-4G depict various compounds with an ethyl attached to thepyridine ring at the nitrogen position.

DETAILED DESCRIPTION OF THE EMBODIMENTS OF THE INVENTION

The foregoing and other aspects of the present invention will now bedescribed in more detail with respect to other embodiments describedherein. It should be appreciated that the invention can be embodied indifferent forms and should not be construed as limited to theembodiments set forth herein. Rather, these embodiments are provided sothat this disclosure will be thorough and complete, and will fullyconvey the scope of the invention to those skilled in the art.

The terminology used in the description of the invention herein is forthe purpose of describing particular embodiments only and is notintended to be limiting of the invention. As used in the description ofthe invention and the appended claims, the singular forms “a,” “an” and“the” are intended to include the plural forms as well, unless thecontext clearly indicates otherwise.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs.

All publications, patent applications, patents and other referencescited herein are incorporated by reference in their entireties for theteachings relevant to the sentence and/or paragraph in which thereference is presented.

The present invention relates to pyridinium derivatives, processes fortheir preparation, methods of their use and compositions comprising suchderivatives. Stilbazium iodide is a known anthelmintic which is reportedto be effective against roundworms, threadworms, and whipworms. U.S.Pat. Nos. 3,075,975 and 3,085,935 recite methods of eradicatinginfestations of parasitic nematodes inhabiting the intestinal tract.This compound can be used to control fungi and/or bacteria forindustrial uses.

One of the embodiments of the present invention includes a compoundcomprising:

or a solvate thereof, wherein X⁻ is an anionic salt, wherein R₁, R₂, R₃,or R₄ are independently selected from the group consisting of methyl,ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear or branched),or wherein when R₁ and R₂ or when R₃ and R₄ are taken together with thenitrogen atom to which they are attached, they form pyrrolidino orpiperidino rings. X⁻ can be selected from the group including fluoride,chloride, bromide, iodide halide, mesylate, tosylate, napthylate,nosylate, para-aminobenzoate, lauryl sulfate, 2,4-dihydroxybenzophenone, 2-(2-hydroxy-5′-methylphenyl)benzotriazole,benzenesulfonate, besylate, ethyl 2-cyano-3,3-diphenyl acrylate and5-butyl phenyl salicylate. R₅ is selected from the group consisting ofmethyl, ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear orbranched), alkynes, n-propyl, i-propyl, n-butyl, i-butyl, substitutedand unsubstituted aryl moieties and substituted and unsubstituted benzylmoieties. R₅ may also be an organometallic compound such as organotin,organosilicon, or organogermanium. Additionally, R₅ may be(CH₂)_(n)-MR₆, wherein n is a number from 1 to 6, M is an organometalliccompound such as tin, silicon, or germanium, and wherein R₆ is aselected from the group consisting of propyl, butyl, or any alkylcompound.

Another embodiment of the present invention includes a compoundcomprising formula (II)

or a solvate thereof, wherein X⁻ is an anionic salt, wherein R₁, R₂, R₃,or R₄ are independently selected from the group consisting of methyl,ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear or branched),or wherein when R₁ and R₂ or when R₃ and R₄ are taken together with thenitrogen atom to which they are attached, they form pyrrolidino orpiperidino rings. X⁻ can be selected from the group including fluoride,chloride, bromide, iodide halide, mesylate, tosylate, napthylate,nosylate, para-aminobenzoate, lauryl sulfate, 2,4-dihydroxybenzophenone, 2-(2-hydroxy-5′-methylphenyl)benzotriazole,benzenesulfonate, besylate, ethyl 2-cyano-3,3-diphenyl acrylate and5-butyl phenyl salicylate. R₅ is selected from the group consisting ofmethyl, ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes (linear orbranched), alkynes, n-propyl, i-propyl, n-butyl, i-butyl, substitutedand unsubstituted aryl moieties and substituted and unsubstituted benzylmoieties. R₅ may also be an organometallic compound such as organotin,organosilicon, or organogermanium. Additionally, R₅ may be(CH₂)_(n)-MR₆, wherein n is a number from 1 to 6, M is an organometalliccompound such as tin, silicon, or germanium, and wherein R₆ is aselected from the group consisting of propyl, butyl, or any alkylcompound. The present compound is more commonly known as stilbazium. Oneof the embodiments of formula I is 2,6,-bis(p-pyrrolidinostyryl)pyridinemethiodide.

Alternatively, the NR₁R₂ and NR₃R₄ moieties may be in various positionsas evidenced in the compounds below.

Another embodiment includes Formula III illustrates the NR₁R₂ moiety inone meta position.

Formula IV illustrates the NR₁R₂ and NR₃R₄ moieties in both metapositions.

may be an anionic salt, R₁, R₂, R₃, or R₄ are independently selectedfrom the group consisting of methyl, ethyl, C₁₋₁₀ alkyl (linear orbranched), alkenes (linear or branched), or wherein when R₁ and R₂ orwhen R₃ and R₄ are taken together with the nitrogen atom to which theyare attached, they form pyrrolidino or piperidino rings. R₅ is selectedfrom the group consisting of methyl, ethyl, C₁₋₁₀ alkyl (linear orbranched), alkenes (linear or branched), alkynes, n-propyl, i-propyl,n-butyl, i-butyl, substituted and unsubstituted aryl moieties andsubstituted and unsubstituted benzyl moieties.

Additionally, the present invention may include compounds of thefollowing general formula V:

or a solvate thereof, wherein n is a number from 1 to 5, wherein Z canbe present at multiple positions on the phenyl ring and is selected fromthe group consisting of C, N, O, S and halogen, wherein X⁻ is an anionicsalt, wherein R₁, R₂, R₃, or R₄ are independently selected from thegroup consisting of nothing, hydrogen, methyl, ethyl, C₁₋₁₀ alkyl(linear or branched), alkenes (linear or branched), nitriles, benzenes,pyridines, benzothiophenes, trifluoroalkyls, difluoroalkyls, substitutedand unsubstituted aryl moieties and substituted and unsubstituted benzylmoieties, or wherein when R₁ and R₂ or when R₃ and R₄ are taken togetherwith the nitrogen atom to which they are attached, they form pyrrolidinoor piperidino rings. X⁻ can be selected from the group includingfluoride, chloride, bromide, iodide halide, mesylate, tosylate,napthylate, nosylate, para-aminobenzoate, benzenesulfonate, besylate,lauryl sulfate, 2,4-dihydroxy benzophenone,2-(2-hydroxy-5′-methylphenyl)benzotriazole, ethyl 2-cyano-3,3-diphenylacrylate and 5-butyl phenyl salicylate. R₅ is selected from the groupconsisting of methyl, ethyl, C₁₋₁₀ alkyl (linear or branched), alkenes(linear or branched), alkynes, n-propyl, i-propyl, n-butyl, i-butyl,substituted and unsubstituted aryl moieties and substituted andunsubstituted benzyl moieties. R₅ may also be an organometallic compoundsuch as organotin, organosilicon, or organogermanium. Additionally, R₅may be (CH₂)_(n)-MR₆, wherein n is a number from 1 to 6, M is anorganometallic compound such as tin, silicon, or germanium, and whereinR₆ is a selected from the group consisting of propyl, butyl, or anyalkyl compound. FIGS. 1-4 illustrate various combinations of thecompounds that may be formed according to the present invention. Thesecompounds can be in the E, E configuration and can be used for any ofthe methods and uses disclosed in the present application.

The compounds of the present invention are capable of existing asgeometric isomers. All such isomers, individually and as mixtures, areincluded within the scope of the present invention for their industrialuses. The E,E isomer is one configuration of the invention, and both thecisoid and transoid 2,6-conformations of the E,E-configuration arepossible. Additionally, the otho, ortho conformation of the structurecan be formed in addition to the para and meta structures illustratedabove. The ortho conformation structure can include the same salts andmoieties as disclosed above and throughout the application.

Some of the embodiments of the present invention include1-ethyl-(E,-E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride, 1-ethyl-(E,-E)-2,6-bis[p-(1-pyrrolidinostyryl]pyridiniumchloride,1-methyl-(E,-E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride and 1-methyl-(E,-E)-2,6-bis[p-(1-pyrrolidinostyryl]pyridiniumchloride.

Compounds according to the invention can be made according to anysuitable method of organic chemistry. More specifically, compounds offormula I can be prepared as outlined in U.S. Pat. No. 3,085,935, thedisclosure of which is incorporated in its entirety.

Additionally, embodiments of the present invention may include thecompounds produced by a synthesis that includes preparing the compoundsby condensation of two equivalents of an aldehyde of formula IV.

with a quaternary ammonium salt of 2,6-lutidine

The condensation may be performed in a lower alcohol with a catalystsuch as a secondary amine (e.g. piperidine). When X⁻ in the aboveformula is an iodide ion (corresponding to an alkiodide salt oflutidine), the condensation product (formula I) is relatively insolubleand precipitates in the course of the reaction. The reaction yield offormula I can be nearly quantitative. Three times the amount of catalystas stated in U.S. Pat. No. 3,085,935 can be used. Other methods may beused to produce the compound and both more or less catalyst may beemployed to produce formula I.

Furthermore, it may be desirable to convert the iodide salt to thechloride salt. This conversion may be accomplished by size exclusion(molecular sieve) chromatography eluted and equilibrated with a suitablesolvent containing an excess of ammonium chloride. The column effluent,containing the chloride salt can be obtained by evaporation of thesolvent, along with the ammonium iodide by-product. The resultingproduct should be substantially free of the iodide salt. Alternatively,alkchloride salt of 2,6-lutidine can be reacted with an aldehyde offormula IV in the presence of a secondary amine (e.g. piperidine) togive the chloride salt of Formula I directly.

The present invention has surprising found that the chloride salt has anincreased stability as compared to the iodide salt. Other methods knownin the art may be utilized to convert the salts to UV blocker salts orsurfactant salts. Other salts may include:

Formula A-Stilbazium p-aminobenzoate salt

Formula B-Stilbazium dodecyl sulfate salt (Stilbazium lauryl sulfatesalt)

Additionally “salts” may include substituted benzophenones such as2,4-dihydroxy benzophenone, substituted benzotriazoles, such as2-(2-hydroxy-5′-methylphenyl)benzotriazole, substituted acrylates, suchas ethyl 2-cyano-3,3-diphenyl acrylate, and salicylates, such as the5-butyl phenyl salicylate.

The salts may include an ultraviolet blocker or a surfactant. As usedherein “ultraviolet blocker” refers to all “photosensitive materials”which refers to all compositions and materials designed to block and/orabsorb ultraviolet light. This term also refers to all photoprotectiveand photoresistant agents.

The compounds of the present invention may be used to treat all areaswhere molds, fungi and bacteria are grown. Examples include, but are notlimited to wood, air ducts, lumber, decks, pipes, stucco, tiles, paint,insulation, roofs, building materials, metal, computer parts, foodpackaging, substrates, etc.

Another embodiment of the present invention can include the stilbaziumcompounds being encapsulated. As used herein the term “microcapsules” isintended to contemplate single molecules, encapsulated discreteparticulate, multiparticulate, liquid multicore and homogeneouslydissolved active components. The encapsulation method may provide eithera water soluble or oil soluble active component encapsulated in a shellmatrix of either a water or oil soluble material. The microencapsulatedactive component may be protected from oxidation and hydration, and maybe released by melting, rupturing, biodegrading, or dissolving thesurrounded shell matrix or by slow diffusion of the active componentthrough the matrix. Microcapsules usually fall in the size range ofbetween 1 and 2000 microns, although smaller and larger sizes are knownin the art.

The compound of the present invention may be placed in a microcapsule orhollow fiber type used for distribution. They may also be dispersed in apolymeric material or held as a liquid.

An active ingredient may be placed with the compound of the presentinvention in a microcapsule. Examples of the active ingredient havingrepellent activity may include triethylene glycol monohexyl ether andN,N-diethyl-m-triamide. Examples of the active ingredient havingaromatic activity include geraniol, limonene, benzyl alcohol, esters ofa C₆₋₂₀ hydrocarbon, ethers, aldehydes and alcoholic compounds. Examplesof the active ingredient having pesticidal activity include insecticidessuch as salithion, diazinon and chlorpyrifos and bactericides such asthiophanate-methyl and captan.

Such constituents can be encapsulated, as is desired in the case ofphase change materials. Such encapsulated constituents can further beencapsulated in microcapsules. The microcapsules can be made from a widevariety of materials, including polyethylene, polypropylenes,polyesters, polyvinyl chloride, tristarch acetates, polyethylene oxides,polypropylene oxides, polyvinylidene chloride or fluoride, polyvinylalcohols, polyvinyl acetates, urethanes, polycarbonates, andpolylactones. Further details on microencapusulation are to be found inU.S. Pat. Nos. 5,589,194 and 5,433,953, the contents of which areincorporated herein in their entirety. Microcapsules suitable for use inthe base materials of the present invention have diameters from about1.0 to 2,000 microns.

No particular limitation is imposed on the shape for holding the activeingredient. In other words, there are various forms for holding theactive ingredient by a holding mixture. Specific examples includemicrocapsules in which the surface of the active ingredient has beencovered with the holding mixture; and products processed into a desiredshape, each being obtained by kneading the active ingredient in theholding mixture or forming a uniform solution of the holding mixture andthe active ingredient, dispersing the active ingredient in the holdingmixture by the removal of the solvent or the like and then processingthe dispersion into a desired shape such as single molecule, liquid,sphere, sheet, film, rod, pipe, thread, tape or chip. In addition, theseprocessed products having a surface covered with a barrier layer forcontrolling the release of the active ingredient and those coated withan adhesive for improving applicability can be given as examples. Asfurther examples, those obtained by filling the active ingredient in theholding mixture processed into a form of a capillary tube, heat sealingboth ends of the capillary tube and then encapsulating the activeingredient therein; and those obtained by centrally cutting theabove-mentioned capillary tube into two pieces, thereby having each oneend as an opening.

The container formed of a holding mixture which container has an activeingredient enclosed therein as a liquid phase to secure uniform releaseability over a long period of time. As such shape, tube-, bottle- orbag-shaped container is used generally.

When the mixture is formed into a container, the sustained release layerdesirably has a thickness of at least 0.002 mm for effecting stablesustained release. There occurs no particular problem when the sustainedrelease layer has a thickness not smaller than 0.002 mm, but thatranging from 0.005 mm to 5 mm can be used. When it exceeds 5 mm, therelease amount of the compound tends to become too small.

For solids, the release surface area of the sustained releasepreparation formed of such a container is desirably 0.001 cm² or larger.A range of from 0.01 cm² to 1 cm² may be used.

When the active ingredient is enclosed and held in a container of thesustained release preparation, said container having been formed of aholding mixture, it may be enclosed in portions. The enclosed amount canbe 0.5 mg to 5 mg, and may be 1 mg, 2 mg, 3 mg, or 4 mg.

As the shape of the container formed of a holding mixture, a tube,bottle and bag can be used. In the case of the tube-shaped preparation,that having an internal diameter of 0.4 mm to 10 mm can be used.Internal diameters smaller than 0.4 mm make it difficult to fill theactive ingredient in the container, while those larger than 10 mm makeit difficult to conduct encapsulation. The bottle-shaped preparation isformed by blow molding or injection molding and generally has aninternal volume of 0.1 to 200 ml. The bottle having an internal volumeless than 0.1 ml cannot be formed easily, while that having an internalvolume greater than 200 ml is not economical because there is a largedifference between the amount of the active ingredient filled thereinand the internal volume. In the case of a bag-shaped preparation, theamount of the active ingredient filled in the bag is desirably 1 mg to100 g.

The biodegradable sustained-release preparation according to the firstgroup of the present invention should retain its essential performanceduring application so that a pigment or dye, or various stabilizers suchas ultraviolet absorber/blocker or antioxidant may be added to theholding mixture in order to improve the weather resistance.Alternatively, it is possible to add such an additive to the activeingredient enclosed in the container formed of a holding mixture.

As used herein, the term “controlled release” is intended to mean therelease of a bio-active at a pre-selected or desired rate. This ratewill vary depending upon the application. Desirable rates include fastor immediate release profiles as well as delayed, sustained orsequential release profiles. Combinations of release patterns, such asinitial spiked release followed by lower levels of sustained release ofthe bio-active are also contemplated by the present invention.

As used herein, the term “bio-active” includes therapeutic agents suchas pharmaceutical or pharmacological active agents, e.g., drugs andmedicaments, as well as prophylactic agents, diagnostic agents and otherchemicals or materials useful in treating or preventing conditions,infections and/or diseases. The compositions of the present inventionare particularly effective in plants and other organisms.

In accordance with the present invention there is provided amicrocapsule bacteriocide and/or fungicide composition comprisingmicrocapsules each having a polyurea shell including as an integral partof said shell a photostable ultraviolet light absorbent compound orblocker compound having a log molar extinction coefficient of from about2 to 5 with respect to radiation having wave lengths in the range offrom about 270 to 350 nanometers and a liquid fill capable of slowlypermeating the shell and comprising a pyridinium salt and a biologicalsynergist therefor.

As used herein “photosensitive material” refers to all compositions andmaterials designed to block and/or absorb ultraviolet light. This termalso refers to all photoprotective and photoresistant agents.

As herein used “surfactant” refers to all compositions includingsurfactant salt compositions that are capable of forming emulsions,micro-emulsions, suspensions, etc.

The entire microcapsule composition can include of 60-90 percent ofliquid fill and 40-10 percent of shell wall, the liquid fill comprising5-40 percent of pyridinium salt, 25-50 percent of biological synergistand 20-40 percent of a water-immiscible organic solvent and the shellincluding as an integral part thereof 0.5-20 percent of photostableultraviolet light absorbent compound (all percentages being based on theweight of the entire microcapsule composition).

The pyridinium salt remains inside the microcapsules while thecomposition is packaged and in storage, i.e., in a closed container dueto the partial pressure of the pyridinium salt surrounding themicrocapsules. When the product is applied as a bacteriocide and/orfungicide, the pyridinium salt, releases slowly (the actual speed ofrelease depending upon the thickness and porosity of the capsule walls).The pyridinium salt is chemically stable during storage and afterapplication until it permeates the capsule walls. At that time itbecomes available as a bacteriocide and/or fungicide until degraded.Since the fill permeates the shell wall slowly, the microcapsule producthas a long effective bacteriocide and/or fungicide life and may bestored for extended periods (e.g. for 6 months and more).

Suitable fill stabilizers absorb ultraviolet radiation in the range ofabout 270-350 nanometers and convert it to a harmless form. They have ahigh absorption coefficient in the near ultraviolet portion of thespectrum (e.g. a log molar extinction coefficient of from about 2 to 5)but only minimal absorption in the visible portion of the spectrum. Theydo not exhibit any substantial chemical reaction with the isocyanategroups and primary amine groups of the shell forming compounds duringthe microencapsulation process. Among the compounds which can be used asfill stabilizers are substituted benzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy benzophenone, 2-hydroxy-4-octyloxybenzophenone, etc.; the benzotriazoles such as2-(2-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-diallyl-2′-hydroxylphenyl)benzotriazole, etc.; substitutedacrylates such as ethyl 2-cyano-3,3-diphenyl acrylate,2-ethylhexyl-2-cyano-3,3-diphenyl acetate, etc.; salicylates such asphenyl salicylates, 5-butyl phenyl salicylate, etc.; and nickel organiccompounds such as nickel bis(octylphenol)sulfide, etc. Additionalexamples of each of these classes of fill stabilizers may be found inKirk-Othmer, Encyclopedia of Chemical Technology. The fill stabilizersmay comprise up to 5 percent, and are generally from about 0.01 to 2percent, by weight of the microcapsule composition.

The embodiments of the invention also provide a process for controllingfungal and bacterial activity by contacting the fungi and bacteria withan effective level of the compositions comprising stilbazium compound asrecited throughout. Contact may be accomplished directly, for example,by atomization of the composition into the air in the form of a spray.Alternatively, compositions of the present invention may be provided invarious other forms, for example in sheet materials carrying themicrocapsules, (e.g. tapes coated or impregnated with the microcapsules)that may be placed in areas where the fungi and bacteria may grow.

Another embodiment of the present invention may include heat sensitivematerials which are excellent in preservation stability especially inresistance to light, and microcapsules having an ultraviolet absorberenclosed therein, which are applicable to various fields. Desirableconstituents which may be present in a base material include materialswhich can absorb heat and protect an underlying material fromoverheating. Thermal energy is absorbed by the phase change of suchmaterials without causing an increase in the temperature of thesematerials. Suitable phase change materials include paraffinichydrocarbons, that is, straight chain hydrocarbons represented by theformula C_(n)H_(n+2), where n can range from 13 to 28. Other compoundswhich are suitable for phase change materials are2,2-dimethyl-1,3-propane diol (DMP),2-hydroxymethyl-2-methyl-1,3-propane diol (HMP) and similar compounds.Also useful are the fatty esters such as methyl palmitate. Phase changematerials that can be used include paraffinic hydrocarbons.

Heat sensitive recording materials are well known which utilize a colorforming reaction between a colorless or light-colored basic dye and anorganic or inorganic color acceptor to obtain record images by thermallybringing the two chromogenic substances into contact with each other.Such heat sensitive recording materials are relatively inexpensive, areadapted for use with recording devices which are compact and easy tomaintain, and have therefore found wide applications as recording mediafor facsimile systems, various computers, etc. In order to improve lightresistance of heat sensitive recording materials a finely dividedultraviolet absorber or blocker can be added to the heat sensitiverecording layer or protective layer.

Another embodiment of the present invention is to provide microcapsuleswhich have excellent retainability of ultraviolet absorber, difficult tobe ruptured at a usual pressure and are excellent in ultraviolet rayabsorbing efficiency.

Embodiments of the present invention can include a heat sensitiverecording material comprising a substrate, a recording layer formed overthe substrate and containing a colorless or light-colored basic dye anda color acceptor, and a protective layer formed over the recordinglayer, the recording material being characterized in that microcapsuleshaving an ultraviolet absorber enclosed therein and having substantiallyno color forming ability are incorporated in the protective layer.

Further, the present invention provides microcapsules having anultraviolet absorber and as required an organic solvent enclosedtherein, which have capsule wall film of synthetic resin and meanparticle size of 0.1 to 3 μm.

The following are examples of ultraviolet absorbers that may be used inthe present invention.

Phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenylsalicylate and like salicylic acid type ultraviolet absorbers;2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone,2,2′-dihydroxy-4-methoxybenzophenone,2,2,′-dihydroxy-4,4′-dimethoxybenzophenone,2-hydroxy-4-methoxy-5-sulfobenzophenone and like benzophenone typeultraviolet absorbers; 2-ethylhexyl 2-cyano-3,3-diphenyt-acrylate, ethyl2-cyano-3,3-diphenylacrylate and like cyanoacrylate type ultravioletabsorbers; bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butyl malonate and likehindered amine type ultraviolet absorbers;2-(2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(2′-hydroxy-5-tert-butylphenyl)benzotriazole,2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)benzotriazole,2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5-tert-butylbenzotriazole,2-(2′-hydroxy-3′,5′-di-tert-amylphenyl)benzotriazole,2-(2′-hydroxy-3′,5′-di-tert-amylphenyl)-5-tert-amylbenzotriazole,2-(2′-hydroxy-3′,5′-di-tert-amylphenyl)-5-methoxybenzotriazole,2-[2′-hydroxy-3′-(3″,4″,5″,6″-tetrahydrophthalimido-methyl)-5′-methylphenyl]benzotriazole,2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole,2-(2′-hydroxy-3′-sec-butyl-5′-tert-butylphenyl)benzotriazole,2-(2′-hydroxy-3′-tert-amyl-5′-phenoxyphenyl)-5-methylbenzotriazole,2-(2′-hydroxy-5′-n-dodecylphenyl)benzotriazole,2-(2′-hydroxy-5′-sec-octyloxyphenyl)-5-phenylbenzotriazole,2-(2′-hydroxy-3′-tert-amyl-5′-phenylphenyl)-5-methoxybenzotriazole,2-[2′-hydroxy-3′,5′-bis(α,α-dimethylbenzyl)phenyl]benzotriazole and likebenzotriazole type ultraviolet absorbers which are solid at ordinarytemperature; 2-(2′-Hydroxy-3′-dodecyl-5′-methylphenyl)-benzotriazole,2-(2′-hydroxy-3′-undecyl-5′-methylphenyl)-benzotriazole,2-(2′-hydroxy-3′-tridecyl-5′-methylphenyl)-benzotriazole,2-(2′-hydroxy-3′-tetradecyl-5′-methylphenyl)-benzotriazole,2-(2′-hydroxy-3′-pentadecyl-5′-methylphenyl)-benzotriazole,2-(2′-hydroxy-3′-hexadecyl-5′-methylphenyl)-benzotriazole,2-[2′-hydroxy-4′-(2″-ethylhexyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(2″-ethylheptyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(2″-ethyloctyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(2″-propyloctyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(2″-propylheptyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(2″-propylhexyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(1″-ethylhexyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(1″-ethylheptyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(1″-ethyloctyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(1″-propyloctyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy-4′-(1″-propylheptyl)oxyphenyl]-benzotriazole,2-[2′-hydroxy4′-(1″-propylhexyl)oxyphenyl]-benzotriazole,2-(2′-hydroxy-3′-sec-butyl-5′-tert-butylphenyl-5-n-butylbenzotriazole,2-(2′-hydroxy-3′-sec-butyl-5′-tert-butylphenyl)-5-tert-pentyl-benzotriazole,2-(2′-hydroxy-3′-sec-butyl-5′-tert-butylphenyl)-5-n-pentyl-benzotriazole,2-(2′-hydroxy-3′-sec-butyl-5′-tert-pentylphenyl)-5-tert-butylbenzotriazole,2-(2′-hydroxy-3′-sec-butyl-5′-tert-pentylphenyl)-5-n-butylbenzotriazole,2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5-sec-butylbenzotriazole,2-(2′-hydroxy-3′,5′-di-tert-pentylphenyl)-5-sec-butylbenzotriazole,2-(2′-hydroxy-3′-tert-butyl-5′-tert-pentylphenyl)-5-sec-butylbenzotriazole,2-(2′-hydroxy-3′,5′-di-sec-butylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-3′,5′-di-sec-butylphenyl)-5-methoxybenzotriazole,2-(2′-hydroxy-3′,5′-di-sec-butylphenyl)-5-tert-butylbenzotriazole,2-(2′-hydroxy-3′,5′-di-sec-butylphenyl)-5-n-butylbenzotriazole, octyl5-tert-butyl-3-(5-chloro-2H-benzotriazole-2-yl)-4-hydroxybenzene-propionate,condensate of methyl3-[3-tert-butyl-5-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate andpolyethylene glycol (molecular weight: about 300) and like benzotriazoletype ultraviolet absorbers which are liquid at ordinary temperature. Ofcourse, the ultraviolet absorber is not limited to thereabove and can beused as required in a mixture of at least two of them.

Although the amount of ultraviolet absorber to be used is not limitedspecifically, the amount can be adjusted to 10 to 500 parts by weight,and generally from to 20 to 250 parts by weight of the ultravioletabsorber versus the active ingredient.

The microcapsules for use in the present invention can be prepared byvarious known methods. They are prepared generally by emulsifying anddispersing the core material (oily liquid) comprising an ultravioletabsorber and, if necessary, an organic solvent in an aqueous medium, andforming a wall film of high-molecular-weight substance around theresulting oily droplets.

Examples of useful high-molecular-weight substances for forming the wallfilm of microcapsules are polyurethane resin, polyurea resin, polyamideresin, polyester resin, polycarbonate resin, aminoaldehyde resin,melamine resin, polystyrene resin, styrene-acrylate copolymer resin,styrene-methacrylate copolymer resin, gelatin, polyvinyl alcohol, etc.Especially, microcapsules having a wall film of a synthetic resin,particularly polyurea resin, polyurethane resin and aminoaldehyde resinamong other resins have excellent retainability of an ultravioletabsorber and high heat resistance and accordingly exhibit theoutstanding additional effect to serve the function of a pigment whichis to be incorporated in the protective layer for preventing sticking tothe thermal head. Moreover, microcapsules having a wall film of polyurearesin or polyurethane resin are lower in refractive index thanmicrocapsules with wall films of other materials and usual pigments, arespherical in shape and are therefore usable favorably because even ifpresent in a large quantity in the protective layer, they are unlikelyto reduce the density of record images (so-called whitening) owing toirregular reflection of light. Further, polyurea resin and polyurethaneresin are more elastic than aminoaldehyde resin and therefore polyurearesin and polyurethane resin are generally used as a wall film formicrocapsules which are used under a condition of high pressure. On theother hand, microcapsules having a wall film made from aminoaldehyderesin have a merit that the wall film can be controlled in thicknesswithout depending on particle size of emulsion because the microcapsulescan be prepared by adding a wall-forming material after emulsificationof a core material.

The present invention may also include organic solvent together with anultraviolet absorber. The organic solvent is not particularly limitedand various hydrophobic solvents can be used which are used in a fieldof pressure sensitive manifold papers. Examples of organic solvents aretricresyl phosphate, octyldiphenyl phosphate and like phosphates,dibutyl phthalate, dioctyl phthalate and like phthalates, butyl oleateand like carboxylates, various fatty acid amides, diethylene glycoldibenzoate, monoisopropylnaphthalene, diisopropylnaphthalene and likealkylated naphthalenes, 1-methyl-1-phenyl-1-tolylmethane,1-methyl-1-phenyl-1-xylylmethane, 1-phenyl-1-tolylmethane and likealkylated benzenes, isopropylbiphenyl and like alkylated biphenyls,trimethylolpropane triacrylate and like acrylates, ester of polyol andunsaturated carboxylic acid, chlorinated paraffin and kerosene. Thesesolvents can be used individually or in a mixture of at least two ofthem. Among these hydrophobic media having a high boiling point,tricresyl phosphate and 1-phenyl-1-tolylmethane are desirable since theyexhibit high solubility in connection with the ultraviolet absorber tobe used in the present invention. Generally, the lower the viscosity ofthe core material, the smaller is the particle size resulting fromemulsification and the narrower is the particle size distribution, sothat a solvent having a low boiling point is conjointly usable to lowerthe viscosity of the core material. Examples of such solvents having alow boiling point are ethyl acetate, butyl acetate, methylene chloride,etc.

The amount of organic solvent to be used should be suitably adjustedaccording to the kind and amount of ultraviolet absorber to be used andthe kind of organic solvent and is not limited specifically. For examplein case of using an ultraviolet absorber which is liquid at ordinarytemperature, an organic solvent is not necessarily used. However, incase of using an ultraviolet absorber which is solid at ordinarytemperature, since it is desired that the ultraviolet absorber be in afully dissolved state in the microcapsules, the amount of organicsolvent, for example in case of microcapsules of polyurea resin orpolyurethane resin, is adjusted generally from to usually 10 to 60 wt.%, or from to 20 to 60 wt. %, based on the combined amount of organicsolvent, ultraviolet absorber and wall-forming material. Further, incase of microcapsules of aminoaldehyde resin, the amount of organicsolvent is adjusted to usually 50 to 2000% by weight, generally from 100to 1000% by weight of ultraviolet absorber.

Additionally, an absorber may be utilized. An absorber should beselected which reduces the sensitivity of the microcapsule in thoseportions of its spectral sensitivity range which interfere with theexposure of microcapsules at other wavelengths (its inactive range)without overly reducing the sensitivity of the microcapsule in thoseportions of the spectral sensitivity range in which the microcapsule isintended to be exposed (its active range). In some cases it may benecessary to balance the absorption characteristics of the absorber inthe active range and the inactive range to achieve optimum exposurecharacteristics. Generally absorbers having an extinction coefficientgreater than about 100/M cm in the inactive range and less than about100,000/M cm in the active range of the microcapsule are used. When theabsorber is directly incorporated into the photosensitive composition,ideally, it should not inhibit free radical polymerization, and itshould not generate free radicals upon exposure.

The absorbers used in the present invention can be selected from amongthose absorbers which are known in the photographic art. Examples ofsuch compounds include dyes conventionally used as silver halidesensitizing dyes in color photography (e.g., cyanine, merocyanine,hemicyanine and styryl dyes) and ultraviolet absorbers. A number ofcolored dyes which absorb outside the desired sensitivity range of themicrocapsules and do not absorb heavily within the range could also beused as absorbers in the present invention. Among these, Sudan I, SudanII, Sudan III, Sudan Orange G, Oil Red O, Oil Blue N, and Fast GarnetGBC are examples of potentially useful compounds.

Additionally ultraviolet absorbers that may be desirable include thoseselected from hydroxybenzophenones, hydroxyphenylbenzo-triazoles andformamidines. The absorbers may be used alone or in combination toachieve the spectral sensitivity characteristics that are desired.

Representative examples of useful hydroxybenzophenones are2-hydroxy-4-n-octoxybenzophenone (UV-CHEK AM-300 from Ferro ChemicalDivision, Mark 1413 from Argus Chemical Division, Witco Chem. Corp., andCyasorb UV-531 Light Absorber from American Cyanamid),4-dodecyl-2-hydroxybenzophenone (Eastman Inhibitor DOBP from EastmanKodak), 2-hydroxy-4-methoxybenzophenone (Cyasorb UV-9 Light Absorberfrom American Cyanamid), and 2,2′-dihydroxy-4-methoxybenzophenone(Cyasorb UV-24 Light Absorber from American Cyanamid). Representativeexamples of useful hydroxybenzophenyl benzotriazoles are2-(2′-hydroxy-5′-methylphenyl)benzotriazole (Tinuvin P from Ciba-GeigyAdditives Dept.),2-(3′,5′-di-tert-butyl-2′hydroxyphenyl)-5-chlorobenzotriazole (Tinuvin327 from Ciba-Geigy), and 2-(2-hydroxy-5-t-octylphenyl)benzotriazole(Cyasorb UV-5411 Light Absorber from American Cyanamid). Representativeexamples of useful formamidines are described in U.S. Pat. No. 4,021,471and include N-(p-ethoxy-carbonylphenyl)-N′-ethyl-N′-phenylformamidine(Givsorb UV-2 from Givaudan Corp.). The optimum absorber andconcentration of absorber for a particular application depends on boththe absorption maximum and extinction coefficient of the absorbercandidates and the spectral sensitivity characteristics of theassociated photoinitiators.

Additionally, the microcapsules, photosensitive compositions,image-forming agents, developers, and development techniques describedin U.S. Pat. Nos. 4,399,209 and 4,440,846, the contents of which areincorporated and may be used in the present invention.

The compounds according to the present invention are also particularlyeffective against powdery mildews and rusts, pyrenophora,rhynchosporium, tapesia, fusarium and leptosphaeria fungi, in particularagainst pathogens of monocotyledonous plants such as cereals, includingwheat and barley. They are furthermore particularly effective againstdowny mildew species, powdery mildews, leaf spot diseases and rusts indicotyledonous plants.

The amount of the compounds of the invention to be applied, will dependon various factors such as the compound employed, the subject of thetreatment (substrate), the type of treatment (e.g. spraying, dusting,seed dressing), the purpose of the treatment (prophylactic ortherapeutic), the type of fungi and/or bacteria to be treated and theapplication time.

The agents may be applied before or after infection of any of thematerials listed by the fungi and/or bacteria.

When applied to the plants the compound of formula I is applied at arate of 25 to 250 g/ha, generally from 50 to 150 g/ha, e.g. 75, 100, 125or 150 g/ha, in association with 20 to 2000 g/ha, generally from 20 to1000 g/ha.

In industrial practice the application rates of the combination dependon the type of effect desired, and range from 0.02 to 3 kg of activeingredient per hectare.

When the active ingredients are used for treating seed, rates of 0.001to 50 g a.i. per kg, and generally from 0.01 to 10 g per kg of seed aregenerally sufficient.

The composition of the invention can be employed in any conventionalform, for example in the form of a twin pack, an instant granulate, aflowable formulation, an emulsion concentrate or a wettable powder incombination with industrially acceptable adjuvants, includingsurfactants such as sodium lauryl sulfate. Such compositions may beproduced in conventional manner, e.g. by mixing the active ingredientswith appropriate adjuvants (diluents or solvents and optionally otherformulating ingredients such as surfactants). Also conventional slowrelease formulations may be employed where long lasting efficacy isintended.

Particularly formulations to be applied in spraying forms such as waterdispersible concentrates or wettable powders may contain surfactantssuch as wetting and dispersing agents, e.g. the condensation product offormaldehyde with naphthalene sulphonate, an alkylarylsulphonate, alignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenoland an ethoxylated fatty alcohol.

A seed dressing formulation is applied in a manner known per se to theseeds employing the combination of the invention and a diluent insuitable seed dressing formulation form, e.g. as an aqueous suspensionor in a dry powder form having good adherence to the seeds. Such seeddressing formulations are known in the art. Seed dressing formulationsmay contain the single active ingredients or the combination of activeingredients in encapsulated form, e.g. as slow release capsules ormicrocapsules.

In general, the formulations include from 0.01 to 90% by weight ofactive agent, from 0 to 20% industrially acceptable surfactant and 10 to99.99% solid or liquid adjuvant(s), the active agent consisting of atleast the compound of formula I, and optionally other active agents,particularly microbides or conservatives or the like. Concentrated formsof compositions generally contain in between about 2 and 80%, generallyfrom between about 5 and 70% by weight of active agent. Applicationforms of formulation may for example contain from 0.01 to 20% by weight,generally from 0.01 to 5% by weight of active agent. Whereas commercialproducts will generally be formulated as concentrates, the end user willnormally employ dilute formulations.

Additionally, the color of the present compounds may be removed by atype of “bleaching”. Furthermore, it has been found possible to bleachthe colored substances leached from the present compound in dyedtextiles and building materials or from textiles and building materialssoiled with a colorant in a solution of wash liquor thereby preventingthe colored substance in question from being deposited on other textilesand building materials in the wash liquor, when enzymes utilizinghydrogen peroxide or molecular oxygen for the oxidation of organic orinorganic substances, including colored substances, are added to thewash liquor. Such enzymes are usually termed peroxidases and oxidases,respectively. It is well recognized in the art (cf. for instance B. C.Saunders et al., Peroxidase, London, 1964, p. 10 ff.) that peroxidasesact on various amino and phenolic compounds resulting in the productionof a color. In view of this, it must be considered surprising thatperoxidases (and certain oxidases) may also exert an effect on coloredsubstances in solution such that dye transfer is inhibited. While themechanism governing the ability of these enzymes to effect dye transferinhibition has not yet been elucidated, it is currently believed thatthe enzymes act by reducing hydrogen peroxide or molecular oxygen andoxidizing the colored substance (donor substrate) dissolved or dispersedin the wash liquor, thereby either generating a colorless substance orproviding a substance which is not adsorbed to the fabric or buildingmaterial.

Additionally, a liquid composition of matter according to the presentinvention may be formed and may be mixed with and/or diluted by anexcipient. When the excipient serves as a diluent, it may be a solid,semi-solid, or liquid material that acts as a vehicle, carrier, ormedium for the composition of matter. Various suitable excipients willbe understood by those skilled in the art and may be found in theNational Formulary, 19: 2404-2406 (2000), the disclosure of pages 2404to 2406 being incorporated by reference herein in their entirety.Preferable excipients include butanedioal and EDTA. Examples of suitableexcipients include, but are not limited to, starches, gum arabic,calcium silicate, microcrystalline cellulose, methacrylates, shellac,polyvinylpyrrolidone, cellulose, water, syrup, and methylcellulose. Anaqueous medium may include an active ingredient or ingredients, aquantity of one or more surfactants sufficient to dissolve or suspendsaid active ingredients uniformly throughout the medium and othermanufacturing additives as known to the art. The latter includegranulating-binding agents such as gelatin; natural gums, such asacacia, tragacanth; starches, sodium alginate, sugars,polyvinylpyrrolidone; cellulose derivatives such ashydroxypropylmethylcellulose, polyvinyloxoazolidones; pharmaceuticalfillers such as lactose, microcrystalline cellulose, dicalciumphosphate, tricalcium phosphate, calcium sulfate, dextrose, mannitol,sucrose; tabletting lubricants if needed such as calcium and magnesiumstearate, stearic acid, talc, sterotex (alkaline stearate). The term“aqueous medium” for one ingredient of one of the embodiments of theinvention is used within the custom of the art. Primarily, it connotes awater medium, with added water-miscible solvents such as isopropanol orethanol when needed, to support the active ingredient.

The present invention is explained in greater detail in the Examplesthat follow. These examples are intended as illustrative of theinvention and are not to be taken are limiting thereof.

EXAMPLE 1 Synthesis of1-Ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumChloride (6)

Step a: Reaction of 2,6-Lutidine (1) and Iodoethane (2) to Form2,6-Lutidine Ethiodide (3). A total of 69.7 grams (0.65 mole) of2,6-lutidine (1) was combined with 202.8 grams of ethyl iodide (2) andthe mixture was heated at 100° C. overnight. The reaction mixture wasthen cooled and the precipitated 2,6-lutidine ethiodide (3) wascollected by filtration. The filtrate was reheated to 100° C. overnight,then cooled and filtered to recover a second crop of solid 2,6-lutidineethiodide (3). These two crops were combined, dissolved in hot absoluteethanol and recrystallized. This resultant solid was dissolved in hotethanol and recrystallized a second time. The purified 2,6-lutidineethiodide (3) was air dried to constant weight to yield 107.5 grams ofdesired product. The ¹H-NMR was consistent with the desired material andthe uncorrected melting point was determined to be 205-206° C.

Step b: Conversion of 2,6-Lutidine Ethiodide (3) to 2,6-LutidineEthochloride (4). The 107.5 grams of 2,6-lutidine ethiodide wasdissolved in 2.0 liters of methanol and the solution was chilled in anice-water bath. A total of 220 grams of anhydrous hydrogen chloride gaswas slowly added to the solution via a gas bubbler. An ice-water bathwas used to keep the reaction temperature below 30° C. during thehydrogen chloride addition. After all the hydrogen chloride had beenadded, the reaction mixture was stirred overnight at room temperature.The reaction mixture was concentrated to near dryness and thenre-dissolved in 1.0 liter of methanol. A total of 103 grams of anhydroushydrogen chloride gas was then bubbled into the mixture. After stirringfor 10 minutes, the reaction mixture was concentrated to dryness undervacuum to yield 94.3 grams of the desired 2,6-lutidine ethochloride (4).

Step c: Reaction of 2,6-Lutidine Ethochloride (4) and4-Pyrrolidinobenzaldehyde (5) to Produce1-Ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumChloride (6). A mixture of 30.6 grams (0.22 mole) of 2,6-lutidineethochloride (4), 75 grams (0.54 mole) of 4-pyrrolidinobenzaldehyde (5),12 mL piperidine and ca. 2 liters of methanol was heated at refluxovernight. The ¹H NMR indicated that no reaction had occurred. Noreaction occurred after heating the reaction mixture for an additional96 hours at reflux. An additional 12 mL of piperidine was added andheating at reflux continued. After a total of 120 hours of heating atreflux, some solids began precipitating but ¹H NMR indicated that thedesired reaction was still incomplete. Another 12 mL of piperidinecatalyst was added and the reaction mixture was heated at reflux for anadditional 24 hours. The ¹H NMR spectrum now indicated the desiredreaction was carried to completion. The reaction mixture was slowlycooled to room temperature and the precipitated solid containing1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride (6) was collected by filtration. The solid was triturated andwashed with three 100 ml portions of ethyl ether to remove impuritiesand residual methanol solvent. The solid was air dried and dried undervacuum to constant weight to yield 32.6 grams of red crystalline1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride (6)—high performance liquid chromatography area percent (HPLCArea %)=98.1%, ¹H NMR (DMSO, d₆); ppm 8.16-8.14 (t, 1H); 8.08-8.07 (d,2H); 7.71-7.68 (d, 1H); 7.69-7.67 (d, 2H, J=8.8 Hz); 7.23-7.20 (d, 1H);6.61-6.59 (d, 2H, J=8.8 Hz); 4.75-4.74 (m, 2H); 3.31 (m, 2H); 1.98-1.96(m, 2H); 1.48-1.45 (t, 3H).

The reaction filtrate was concentrated to approximately one-half theoriginal volume, 10 mL of piperidine was added and the dark reactionfiltrate was heated at reflux for 24 hours. ¹H NMR spectral analysisindicated that more1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride (6) had formed, possibly by olefinic isomer equilibration. Theheat was removed and the reaction mixture was allowed to stir at roomtemperature for 48 hours, during which time a precipitate formed. Thesolid was collected by filtration and was triturated and washed withthree 100 ml portions of ethyl ether to remove impurities and residualmethanol solvent. The red crystalline solid was air dried and driedunder vacuum to constant weight to yield 19.2 grams of additional1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride (6)—HPLC Area %=97.4%, ¹H NMR was consistent with the firstcrop of product (6).

EXAMPLE 2 Synthesis of1-Ethyl-(E,E)-2,6-bis[2-[4-(dimethylamino)phenyl]ethenyl]pyridiniumChloride

A mixture of 9.0 grams (0.07 mole) of 2,6-lutidine ethochloride, 23.6grams (0.16 mole) of 4-dimethylaminobenzaldehyde, 14 mL piperidine and350 mL methanol was heated at reflux for 77 hours. After 77 hr atreflux, high performance liquid chromatography—mass spectral analysis(LC/MS analysis) indicated that the desired product was present in thereaction mixture. The reaction mixture was slowly cooled to effectprecipitation and the precipitated solids were collected by filtration.The solids were triturated and washed with three 100 ml portions ofethyl ether to remove impurities and residual methanol solvent. Thesolid was air dried and dried under vacuum to constant weight to yield2.8 grams of red crystalline1-ethyl-(E,E)-2,6-bis[2-[4-(dimethylamino)phenyl]ethenyl]pyridiniumchloride—high performance liquid chromatography area percent (HPLC Area%)=99.5%, ¹H NMR (DMSO, d₆) consistent with the desired product.

The reaction filtrate was concentrated to approximately one-half theoriginal volume. A total of 10 mL of piperidine catalyst was added andthe dark solution was heated at reflux for an additional 24 hours. Atthis point high performance liquid chromatography area percent analysis(HPLC A% analysis) indicated that more product had formed and the2,6-lutidine ethochloride starting material was almost gone. The heatwas removed and the reaction was concentrated under vacuum to yield aheavy slurry. The precipitated solid was collected by filtration, washedwith three 100 ml portions of ethyl ether and the resulting solid wasair dried and vacuum dried overnight to yield 13.6 grams of redcrystalline1-ethyl-(E,E)-2,6-bis[2-[4-(dimethylamino)phenyl]ethenyl]pyridiniumchloride—HPLC Area %=99%, ¹H NMR was consistent with the desiredproduct.

EXAMPLE 3 Synthesis of1-Ethyl-(E,E)-2,6-bis[2-[4-(diethylamino)phenyl]ethenyl]pyridiniumChloride

A mixture of 9.0 grams (0.07 mole) of 2,6-lutidine ethochloride, 28.1grams (0.16 mole) of 4-diethylaminobenzaldehyde, 14 mL piperidine and350 mL methanol was heated to reflux for 96 hours at which time LC/MSanalysis indicated that the desired product was present. The reactionmixture was cooled and concentrated under vacuum to produce a slurry.The solid was collected by filtration and was triturated and washed withthree 50 ml portions of ethyl ether. The resulting purified solid wasair dried and vacuum dried to yield 17.3 grams of red crystalline1-ethyl-(E,E)-2,6-bis[2-[4-(diethylamino)phenyl]ethenyl]pyridiniumchloride—high performance liquid chromatography area percent (HPLC Area%)=95%, ¹H NMR (DMSO, d₆) was consistent with the desired material and atrace of the starting 4-diethylaminobenzaldehyde present.

EXAMPLE 4 Synthesis of1-Ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridinium4-Aminobenzoate Salt

A total of 52.8 g (0.12 mole) of1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride and 18.6 grams (0.12 mole) of the sodium salt of 4-aminobenzoicacid (sodium salt of p-aminobenzoic acid, Na⁺ PABA⁻) were dissolved in1.3 liters of methanol and this mixture was allowed to stir at roomtemperature for 4 days during which time a precipitate formed. Thereaction mixture was then filtered and the solid salt was air dried andvacuum dried to yield a first crop of 28.0 grams of1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridinium4-aminobenzoate salt (also termed the PABA salt). The filtrate wasconcentrated under vacuum to produce more precipitate. Isolation of thesecond crop was effected by filtration followed by air drying and vacuumdrying of the solid to afford a second crop of 42.6 grams of1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridinium4-aminobenzoate salt (also termed the PABA salt)—high performance liquidchromatography area percent (HPLC A%) first crop=99.6% excluding PABA;HPLC A% second crop=99.9% excluding PABA; ¹H NMR and Mass Spectralanalyses for both crops were consistent with structure of the desiredmaterial1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridinium4-aminobenzoate salt. This product is also named1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniump-aminobenzoate salt or1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridinium PABAsalt.

By the methods demonstrated in Examples 1-3, substituted andunsubstituted aromatic aldehydes or substituted and unsubstitutedheteroaromatic aldehydes are reacted with substituted and unsubstitutedlutidine ethochloride salts, lutidine isobutochloride salts, lutidinemethochloride salts, lutidine 1,1,1-trifluoroethochloride salts and thelike and with secondary amine catalysts such as piperidine andpyrrolidine in polar protic solvents such as methanol, ethanol,2-propanol and the like or polar aprotic solvents such as acetonitrile(ACN), dimethyl acetamide (DMA), dimethyl formamide (DMF), dimethylsulfoxide (DMSO) and the like to yield any possible combination ofcompounds as noted throughout the application and the claims. Applicantshave additionally provided numerous compounds shown in FIGS. 1-4 toillustrate some of the possible combinations of the present invention.

In the following Examples, the “active ingredient” may be any compoundof formula (I) as recited above or a pharmaceutically acceptable salt orsolvate thereof.

EXAMPLE 5 Antibacterial Activity

Solutions of formula I, stilbazium chloride, (1% dimethylsulfoxide) werediluted with sterile water, using serial half-step dilutions. Fortymicroliters of each dilution were then pipetted onto seededMueller-Hinton agar plates. The agar plates were then incubated for 24hours at 35° C. and zones of inhibition were then recorded. The MinimumInhibitory Concentration (MIC) was the lowest concentration of the testmaterial which produced a zone of inhibition against the organism. TheMIC for formula I against a series of organisms is listed in the tablebelow.

TABLE 1 Anti-bacterial activity of formula I Strain MIC Streptococcuspyogenes 1.0 Streptococcus faecalis 1.0 Streptococcus algalactia 1.0Staphylococcus aureus 0.3 Bordella bronchiseptica 1.0 Vibrio cholerae10.0 Pasturella multocida 3.0 E. coli >100 Pseudomonas aerugenosa >100 *The data represent the minimal inhibitory concentrations of formula I,in μg/mL, for inhibition of bacterial growth, cultured in vitro.

EXAMPLE 6 Antifungal Activity

Fungal strains (obtained from ATCC) were grown in Mueller-Hinton brothfor 18 hours at 35° C. Plates were then seeded with the broth cultureand allowed to air-dry at room temperature (22° C.) for about 10-15minutes. Forty microliters of formula I (in 1% dimethylsulfoxide) andserial half-step dilutions in water were then pipetted onto the seededMueller-Hinton agar plates. The plates were then incubated for 24 hoursat 35° C. and zones of inhibition were then recorded. The MinimumInhibitory Concentration (MIC) was the lowest concentration of formula Iwhich produced a zone of inhibition against the organism. The followingtable lists the antifungal activity of formula I against various fungalstrains.

TABLE 2 Inhibition of yeast and fungal growth by Formula I in vitroOrganism MIC Candida albicans <0.006 Candida tropicalis <0.4Cryptococcus neoformans <0.4 Saccharomyces cervisciae <0.4 Aspergillusfumigatus <0.006 Aspergillus flavus 6.25 Fusarium solani <0.4 Rhizopusarrihizus 6.25 Microsporidium canis 1.6 Microsporidium gypseum 1.6Trichophyton equinium 1.6 Trichophyton mentagrophyt 1.6 Trichophytonrubrum 1.6 Epidermophyton floccsum 1.6 * The data represent the minimalinhibitory concentrations of formula I, in μg/mL, for inhibition ofbacterial growth, cultured in vitro.

EXAMPLE 7

Stilbazium iodide was tested against a panel of plant relevant moldstains. A stock solution of the compound was prepared in DMSO at aconcentration of 10,000 ppm a.i. Further dilutions were prepared withwater. The test was conducted at the following concentrations: 125, 31,8, 21, 0.5 and 0.125 ppm a.i. Spore suspensions of the fungi wereprepared. The test was conducted in microtiter plates and for eachfungus and each concentration, 3 wells were prepared. Incubation of theinoculated plates was carried out at 18° C. for 7 days. After this time,the optical density of the mycelium developed in each well was measuredat 405 nm.

The data produced, shown in Table 3, allowed an assessment of the IC 90value (the concentration at which the fungal growth was reduced by atleast 90% compared to the control).

TABLE 3 Organism Plant Relevance IC90 Alternaria solani Potato >125Botrytis cinerea Vegetable 0.5 Cochliobolus mijabeanus Corn >125Colletotrichum lagenarium Mellons 31 Fusarium culmorum Wheat Head >125Phytophthora infestans Tomato 2 Pyrenophora teres Barley 31 Pyriculariaoryzae Rice 8 Rhizoctonia solani Rice Sheath 2 Septonia tritici WheatLeaf 2

EXAMPLE 8

The data shown below in Table 4 illustrates various bacteria and fungithat can be treated by stilbazium compounds. The data illustrates theoverall effectiveness of various stilbazium compounds.

TABLE 4 Isolate MIC MIC Species # 80% 100% MFC Alternaria species 128.896.25 12.5 >100 Aspergillus flavus 112.96 3.12 6.25 6.25 Aspergillusflavus 194.99 3.12 3.12 12.5 Aspergillus flavus 107.96 6.25 12.5 25Aspergillus flavus 141.88 12.5 25 25 Aspergillus flavus 178.03 12.525 >25 Aspergillus flavus 173.03 25 25 >25 Aspergillus fumigatus 168.953.12 6.25 >25 QC A. fumigatus 168.95 3.12 6.25 >100 QC A. fumigatus168.95 3.12 6.25 >100 Aspergillus fumigatus 111.02 3.12 6.25 12.5Aspergillus fumigatus 153.90 12.5 25 25 Aspergillus fumigatus 182.9912.5 25 >25 Aspergillus sydowii 165.02 0.78 1.56 3.12 Aspergillusversicolor 120.02 1.56 3.12 6.25 Bipolaris spicifera 155.89 3.123.12 >100 Candida albicans A39 0.39 0.39 0.39 Candida albicans 117.000.39 0.39 0.39 QC C. albicans 117.00 1.56 1.56 3.12 QC C. albicans117.00 3.12 3.12 6.25 Candida albicans 117.00 0.78 1.56 3.12 Candidaalbicans 116.98 0.39 0.39 1.56 Candida albicans 126.97 0.39 0.78 0.78Candida albicans 149.97 0.39 0.39 0.78 Candida albicans 159.95 0.39 0.391.56 Candida albicans 156.97 1.56 1.56 1.56 Candida albicans 203.03 1.561.56 3.12 Candida albicans 204.03 1.56 1.56 1.56 Candida albicans 205.031.56 1.56 6.25 Candida albicans 206.03 3.12 3.12 12.5 Candida albicans202.03 3.12 3.12 3.12 Candida parapsilosis 110.01 0.78 0.78 3.12 Candidaparapsilosis ATCC 22019 0.78 0.78 3.12 Candida parapsilosis 109.96 1.561.56 3.12 Candida parapsilosis 118.02 1.56 1.56 6.25 Candidaparapsilosis 123.00 1.56 1.56 6.25 Chaetomium species T 217 1.563.12 >100 Cryptococcus neoformans H99 0.012 0.024 1.56 Curvularia lunata141.90 1.56 3.12 >100 Curvularia lunata 110.90 3.12 3.12 >100 Curvularialunata v. aerie 104.89 3.12 6.25 >100 Curvularia lunata 146.90 6.256.25 >100 Penicillium aurantiogris- 135.02 6.25 12.5 >100 eumPenicillium chrysogenum 119.02 0.78 0.78 12.5 Rhizopus oryzae 172.861.56 6.25 >100 Rhizopus oryzae 182.88 3.12 6.25 >100 Rhizopus oryzae318.86 3.12 6.25 >100 Rhizopus oryzae 117.89 6.25 6.25 12.5 Rhizopusoryzae 127.88 12.5 12.5 >25 Rhizopus oryzae 181.88 12.5 12.5 >25Rhodotorula mucilaginosa 213.03 1.56 3.12 6.25 Rhodotorula mucilaginosa207.03 3.12 3.12 3.12 Rhodotorula mucilaginosa 209.03 3.12 6.25 6.25Rhodotorula mucilaginosa 210.03 3.12 3.12 3.12 Rhodotorula mucilaginosa211.03 6.25 6.25 6.25

In the specification, there has been disclosed typical preferredembodiments of the invention and, although specific terms are employed,they are used in a generic and descriptive sense only and not forpurposes of limitation of the scope of the invention being set forth inthe following claims.

1. An encapsulated formulation comprising a compound having the formula:

wherein the NR₁R₂ and NR₃R₄ moieties are in the ortho, meta or paraposition; wherein X⁻ is an anionic salt; wherein R₁, R₂, R₃, or R₄ areindependently selected from the group consisting of C₁₋₁₀ alkyl (linearor branched), alkenes (linear or branched), or wherein R₁ and R₂ or R₃and R₄ taken together with the nitrogen atom to which they are attachedform pyrrolidino or piperidino rings; wherein R₅ is selected from thegroup consisting of C₁₋₁₀ alkyl (linear or branched), alkenes (linear orbranched), alkynes, substituted and unsubstituted aryl moieties andsubstituted and unsubstituted benzyl moieties and the encapsulatedformulation is a controlled-release formulation.
 2. The encapsulatedformulation of claim 1 further comprising an excipient and aphotosensitive material.
 3. The encapsulated formulation of claim 1 or2, wherein the encapsulated formulation is a microcapsule.
 4. Theencapsulated formulation of claim 2, wherein the photosensitive materialabsorbs ultraviolet radiation.
 5. The encapsulated formulation of claim2, wherein the photosensitive material blocks ultraviolet radiation. 6.The microcapsule encapsulated formulation of claim 3, wherein thecompound is (a) protected from oxidation and hydration, (b) released bymelting, rupturing or biodegrading, (c) released by dissolving asurrounded shell matrix, and/or (d) released by slow diffusion ofcomposition through the shell matrix.
 7. An encapsulated formulationcomprising a compound selected from the group consisting of1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride,1-ethyl-(E,E)-2,6-bis[2-[4-(dimethylamino)phenyl]ethenyl]pyridiniumchloride,1-ethyl-(E,E)-2,6-bis[2-[4-(diethylamino)phenyl]ethenyl]pyridiniumchloride,1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridinium4-aminobenzoate salt and1-methyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride, wherein the compound is substantially free of any otherconfigurational isomers.
 8. The encapsulated formulation of claim 7further comprising an excipient and a photosensitive material.
 9. Theencapsulated formulation of claim 7, wherein the encapsulatedformulation is a microcapsule.
 10. An encapsulated formulationcomprising a compound having the formula:

said compound is in an E, E configuration, and wherein NR₁R₂ and NR₃R₄are in the ortho, meta or para position; X⁻ is an anion; R₁, R₂, R₃, orR₄ are independently selected from the group consisting of C₁₋₁₀ alkyl(linear or branched), alkenes (linear or branched), or wherein R₁ and R₂or R₃ and R₄ taken together with the nitrogen atom to which they areattached form pyrrolidino or piperidino rings; and R₅ is (CH₂)_(n)-MR₆,wherein n is a number from 1 to 6, M is an organometallic compoundselected from the group consisting of tin, silicon, and germanium, andwherein R₆ is alkyl, substituted or unsubstituted.
 11. The compound ofclaim 10, wherein X³¹ is selected from the group consisting of fluoride,chloride, bromide, iodide halide, mesylate, tosylate, napthylate,nosylate, para-aminobenzoate, lauryl sulfate, 2,4-dihydroxybenzophenone, 2-(2-hydroxy-5′-methylphenyl) benzotriazole,benzenesulfonate, besylate, ethyl 2-cyano-3,3-diphenyl acrylate and5-butyl phenyl salicylate.
 12. The encapsulated formulation of claim 10,wherein M is silicon.
 13. The encapsulated formulation claim 10, furthercomprising an excipient and a photosensitive material.
 14. Theencapsulated formulation of claim 10 or 13, wherein the encapsulatedformulation is a microcapsule.
 15. The encapsulated formulation of claim13, wherein the photosensitive material absorbs ultraviolet radiation.16. The encapsulated formulation of claim 13, wherein the photosensitivematerial blocks ultraviolet radiation.
 17. The encapsulated formulationof claim 15, wherein the compound is (a) protected from oxidation andhydration, (b) released by melting, rupturing or biodegrading, (c)released by dissolving a surrounded shell matrix, and/or (d) released byslow diffusion of composition through the shell matrix.
 18. Amicrocapsule comprising: a compound selected from the group consistingof 1-ethyl-(E,E)-2,6-bis[2-[4-pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride,1-ethyl-(E,E)-2,6-bis[2-[4-(dimethylamino)phenyl]ethenyl]pyridiniumchloride,1-ethyl-(E,E)-2,6-bis[2-[4-(diethylamino)phenyl]ethenyl]pyridiniumchloride,1-ethyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridinium4-aminobenzoate salt and1-methyl-(E,E)-2,6-bis[2-[4-(pyrrolidinyl)phenyl]ethenyl]pyridiniumchloride, wherein the compound is substantially free of any otherconfigurational isomers; and an excipient and a photosensitive material,wherein a ratio of the photosensitive material to the compound is 1:10.19. A composition comprising the encapsulated formulation of claim 1.20. A composition comprising the encapsulated formulation of claim 3.21. A composition comprising the encapsulated formulation of claim 7.22. A composition comprising the encapsulated formulation of claim 9.23. A composition comprising the encapsulated formulation of claim 10.24. A composition comprising the encapsulated formulation of claim 14.25. A composition comprising a microcapsule of claim
 15. 26. A method ofcombating fungi and/or bacteria in wood, air duct, paint, sheetrock,food packaging, or food products, wherein said method comprisesadministering to said wood, air duct, paint, sheetrock, food packaging,or food product an effective amount of a compound comprising:

wherein the NR₁R₂ and NR₃R₄ moieties are in the ortho, meta or paraposition; wherein X³¹ is an anionic salt; wherein R₁, R₂, R₃, or R₄ areindependently selected from the group consisting of C₁₋₁₀ alkyl (linearor branched), alkenes (linear or branched), or wherein R₁ and R₂ or R₃and R₄ taken together with the nitrogen atom to which they are attachedform pyrrolidino or piperidino rings; and wherein R₅ is selected fromthe group consisting of C₁₋₁₀ alkyl (linear or branched), alkenes(linear or branched), alkynes, substituted and unsubstituted arylmoieties and substituted and unsubstituted benzyl moieties, and whereinthe compound is encapsulated.
 27. The method of claim 26, wherein thecompound is encapsulated in a microcapsule.
 28. A method for treating anindustrial product with fungal growth that comprises administering tothe site where growth is to be treated an effective amount of a compoundcomprising:

wherein the NR₁R₂ and NR₃R₄ moieties are in the ortho, meta or paraposition; wherein X³¹ is an anionic salt; wherein R₁, R₂, R₃, or R₄ areindependently selected from the group consisting of C₁₋₁₀ alkyl (linearor branched), alkenes (linear or branched), or wherein R₁ and R₂ or R₃and R₄ taken together with the nitrogen atom to which they are attachedform pyrrolidino or piperidino rings; and wherein R₅ is selected fromthe group consisting of C₁₋₁₀ alkyl (linear or branched), alkenes(linear or branched), alkynes, substituted and unsubstituted arylmoieties and substituted and unsubstituted benzyl moieties, and whereinthe compound is encapsulated.
 29. The method of claim 28, wherein thecompound is encapsulated in a microcapsule.
 30. A method for treating anindustrial product with fungal growth that comprises administering tothe site where growth is to be treated an effective amount of a compoundcomprising:

said compound is in an E, E configuration, and wherein NR₁R₂ and NR₃R₄are in the ortho, meta or para position; X⁻ is an anion; R₁, R₂, R₃, orR₄ are independently selected from the group consisting of C_(mo)alkyl(linear or branched), alkenes (linear or branched), or wherein R₁ and R₂or R₃ and R₄ taken together with the nitrogen atom to which they areattached form pyrrolidino or piperidino rings; and R₅ is (CH₂)_(n)-MR₆,wherein n is a number from 1 to 6, M is an organometallic compoundselected from the group consisting of tin, silicon, and germanium, andwherein R₆ is alkyl, substituted or unsubstituted, and wherein thecompound is encapsulated.
 31. The method of claim 30, wherein M issilicon.
 32. The method of claim 30, wherein the compound isencapsulated in a microcapsule.
 33. A method of controlling fungi and/orbacteria comprising administering a composition comprising:

wherein the NR₁R₂ and NR₃R₄ moieties are in the ortho, meta or paraposition; wherein X″ is an anionic salt; wherein R₁, R₂, R₃, or R₄ areindependently selected from the group consisting of C₁₋₁₀ alkyl (linearor branched), alkenes (linear or branched), or wherein R₁ and R₂ or R₃and R₄ taken together with the nitrogen atom to which they are attachedform pyrrolidino or piperidino rings; and wherein R₅ is selected fromthe group consisting of methyl, ethyl, C₁₋₁₀ alkyl (linear or branched),alkenes (linear or branched), alkynes, substituted and unsubstitutedaryl moieties and substituted and unsubstituted benzyl moieties, andwherein the compound is encapsulated.
 34. A method of controlling fungiand/or bacteria comprising administering a composition comprising:

said compound is in an E, E configuration, and wherein NR₁R₂ and NR₃R₄are in the ortho, meta or para position; X⁻ is an anion; R₁, R₂, R₃, orR₄ are independently selected from the group consisting of C₁₋₁₀ alkyl(linear or branched), alkenes (linear or branched), or wherein R₁ and R₂or R₃ and R₄ taken together with the nitrogen atom to which they areattached form pyrrolidino or piperidino rings; and R₅ is (CH₂)_(n)-MR₆,wherein n is a number from 1 to 6, M is an organometallic compoundselected from the group consisting of tin, silicon, and germanium, andwherein R₆ is alkyl, substituted or unsubstituted, and wherein thecompound is encapsulated.
 35. The method of claim 34, wherein M issilicon.
 36. The method of claim 33 or 34, wherein the compound isencapsulated in a microcapsule.
 37. The method of claim 33 or 34,wherein said method of controlling fungi and/or bacteria furthercomprises binding and containing the fungi and/or bacteria in the samearea.
 38. The method of claim 33 or 34, wherein said compound isadministered before fungal growth occurs.
 39. The method of claim 33 or34, wherein said composition is administered to a substrate.
 40. Themethod of claim 39, wherein said substrate is selected from the groupconsisting of sheetrock, lumber, decking, flooring, roofing, carpets,wallpaper, paneling, cloth caulking, mortar, tiles, grout, fasteners,adhesives, paint, coatings, sealants and stucco.
 41. The method of claim33 or 34, wherein said method further comprises administering saidcomposition to a food packaging system to control fungi and/or bacteriaby reducing fungal and/or bacterial growth.
 42. The method of claim 33or 34, wherein said method further comprises administering saidcomposition to a medicinal product to control fungi and/or bacteria byreducing fungal and/or bacterial growth.
 43. The method of claim 41,wherein said food packaging system is selected from the group consistingof plastic, paper and foam.
 44. A method of controlling insectscomprising administering an effective amount of a compound comprising:

wherein the NR₁R₂ and NR₃R₄ moieties are in the ortho, meta or paraposition; wherein X⁻ is an anionic salt; wherein R₁, R₂, R₃, or R₄ areindependently selected from the group consisting of C₁₋₁₀ alkyl (linearor branched), alkenes (linear or branched), or wherein R₁ and R₂ or R₃and R₄ taken together with the nitrogen atom to which they are attachedform pyrrolidino or piperidino rings; and wherein R₅ is selected fromthe group consisting of C₁₋₁₀ alkyl (linear or branched), alkenes(linear or branched), alkynes, substituted and unsubstituted arylmoieties and substituted and unsubstituted benzyl moieties, and whereinthe compound is encapsulated.
 45. The method of claim 44, wherein thecompound is encapsulated in a microcapsule.
 46. A method of controllinginsects comprising administering an effective amount of a compoundcomprising:

said compound is in an E, E configuration, and wherein NR₁R₂ and NR₃R₄are in the ortho, meta or para position; X″ is an anion; R₁, R₂, R₃, orR₄ are independently selected from the group consisting of C₁₋₁₀ alkyl(linear or branched), alkenes (linear or branched), or wherein R₁ and R₂or R₃ and R₄ taken together with the nitrogen atom to which they areattached form pyrrolidino or piperidino rings; and R₅ is (CH₂)_(n)-MR₆,wherein n is a number from 1 to 6, M is an organometallic compoundselected from the group consisting of tin, silicon, and germanium, andwherein R₆ is alkyl, substituted or unsubstituted, and wherein thecompound is encapsulated.
 47. The method of claim 46, wherein M issilicon.
 48. The method of claim 46, wherein the compound isencapsulated in a microcapsule.